Complex cobalt compounds



United States Patent -CONIPLEX COBALT ECQIVIPOUNDS Arthur Bnehler,Rheinfelden, Switzerland, .assignor to CibaLimited,,Basel, Switzerland,2 Swiss firm No Dra'wing. ApplicationFebruary- 5,1954 .SerialNo. 408,587

Claims; priority,.applicationswitzerland February 11,:1953 Glaims. '(Cl.260-145) represents a naphthalene radical :which is bound to the azolinkage in ZLPOSlllOI] .vicinalto .the -NH-Y group.

Especially valuable ,are those cobalt compounds which contain one atomofcobalt boundin complex union to two molecules of monoazo-dyestuifs, .andespecially :those cobalt compounds of .this constitution whichecontain amonoazo-dyestufi ,containing a :sulfone group or a sulfonicacid amide,group.

'The invention also includes a process for making the above cobaltcompoundsb'y treating a monoazo-dyestuti of the above Formula 1 with anagent yielding cobalt. I'

The monoazo-dyestuifs of the above formula used as starting materialsinthe process of this invention can be obtained from ortho-hydroxyrdiazocompounds free from sulfonic acid and carboxylic acidzgroups,advantageously suchrcompounds of the'benzene series,vand from aminonaphthalenes capable of coupling in ;a,position vicinal to a secondaryamino group and also free from sulfonic acid and carboxylic acid groups.As diazo-compounds there may be mentioned above all those which'containas a substituent a nitro group and/or a sulfone group or a sulfonic acidamide group or both of the two latter groups. As examples oflsuchdiam-compounds there may be mentioned those obtainable from thefollowing amines:

'Z-amino-l hydroxybenzenelor r5-methyl sulfone,

2 amino-,1 -'hydroxybenzene 4 or 5 --ethyl sulfone,-'4 chloro '2 amino'l hydroxybenz'ene 6- methyl sulfone,'6 chloro -2 amino 1 hydroxybenzene4.- methylsulfone,' 2 amino l hydroxybenzene- 4 or 5 n propyl sulfone, 2amino 1 hydroxybenzene 4 or 5 isopropyl sulfone, 2 amino 1hydroxybenzene -4 -"or'- 5 -'n butyl-sulfone, 2 amino 1- hydroxy- 4chlorobenzene 6 phenyl sulfone, and also 3 amino 4 hydroxy diphenylsulfone, 3' amino --4- hydroxy diphenyl x sulfone acid amide, 4 amino 3-hydroxydiphenyl sulfone, 2 amino l hydroxybenzenex4 or 5 vbenzylsulfone, 3 amino 4.-.hydroxy 4'- methyl 1:1 diphenyl sulfone, 7-3 amino4 ,-hydroxy- 4' methoxy 1:1 diphenyl sulfone, 4 amino 3 hydroxy 4'methyl 1:1 diphenylsulfone, 3 amino- 4 hydroxy 4 chloro 1:1 diphenylsulfone, 6- nitro 2 amino l hydroxybenzene 4 sulfonic acid- N phenylamide 4' methyl sulfone, and especially 2 amino 1 hydroxybenzene 4 or 5sulfonic acid amide and the corresponding -methyl-, -ethyl-,-isopropyl-, -n-buty1-, -secondary butyl-, -tertiary butyl-,-hydroxyethyl-, -benzyl-, -cyclohexylor -phenylamide, and

also *the corresponding -'dimethyl-, -'dietliyl-, --dibutyl-,

2 -N-methyl-N fl-hydroxyethyb, -N-methylph enylor -N- ethyl phenyl-amides, 4 chloro -"2 amino 1 hydroxybenzene 6 sulfonic acid amide, 4methoxy 2- amino 1 hydroxybenzene '5 sulfonic acid amide, 4 chloro 2amino 1 hydroxybe-nzene 5 sulfonic acid amide, 6 chloro 2 amino 1hydroxybenzene- 4 sulfonic acid amide or advantageously-thefollowingcompounds containingsnitro groups, 4 nitro -z2-- amino- 1 hydroxybenzene6 methyl sulfone, 6,- 'nitro:- 2- amino 1 hydroxybe'nzene --4'metliyl'isulfone, 2.:- amino 1 hydroxy 6 nitrobenzene---4 v phenylsultone, 2 amino 1 hydroxy '4 nitrobenzene -6- phenyl sulfone, 2 amino1.- hydroxy,- 6.--nitrobenzene- 4 benzyl sulfone,..Z- amino ;1 :hydroxy4.--nitrobenzone --6 benzyl sulfone, 6 nitro -':2.- amino 11-hydroxybenzene -:4 --.sulfonic acid amideor 4 nitro 2- amino 1hydroxybenzene 6 sulfonicacid amide and the corresponding -alkyl-,'.-hydroxyalkyl-, PN-alkyI-N- hydroxylalky1-, or phenyl-amides; andalso'compoun'ds free from sulfonesand sulfoniclacidramide groups,whichare advantageously coupled with coupling components containing sulfoneor sulfonic acid amide groups,-'such=as 4,-nitro-, 4-chloroor 4-methoxy2-amino l hydroxybenzene, 3-aminc-4 hydroxyacetophenone, 4:6-dichloro-2-amino-l-hydroxybenzene, :4=methoxy-5-chloro-2-amino 1- hydroxybenzeneand advantageously 5-nitro-2-amino- 1- hydroxybenzene,4-chloro-5-nitro-2i-amino-Lhydroxyben- 'zene, 4-nitro-6Fchloro-2amino-l-hydroxybenzene, 4 nitro-6,-acetylarnino-2-amino-l-hydroxybenzene,6-nitro-'4-acetylamino-Z-amino-l-hydroxybenzene, :or 36-nitro-4-chlo'ro-2 amino 1 -hydroxybenzene, 94:6 -:dinitro 2 -=amin'ol-hydroxybenzene.

As coupling components there come into consideration secondarynaphthylamines which are-free irom sulfonic acid :and carboxylic acid:groups end-are capable of coupling in a position -vicinal to the aminogroup. Above all there may be mentioned amino naphthalene compounds of'thiskind -of.which the amino-group is substituted by an alkyl radicalor advantageously an aryl radical which may contain substituents, forexample: l-phenyla'minonaphtha'lenei-methyl sulfone, 1benzylaminonaphthalene- 4-sulfonic acid amide,1-phenylaminonaphthalenel-sulfonic .acid amide,l-phenylaminonaphthalenet-sulfonic acid methylor -phenylamide, andadvantageously ,8- napht-hylamine derivatives, such as2-methylaminonaphthalene, Z hydroXyethyl-aminonaphthalene,2-ph'enylaminonaphthalene, 2-phenylaminonaphthalene-methyl sulfone,2-phenylaminonaphthalene 6-sulfonic acid amide,

2 p'henylarninonaphthalene 6 -.sulfonic acid isopropylamide,Z-phenylaminonaphthalene-Z-, -3'- or -4'-sulfonic acid amide,Z-phenylaminonaphthalene-2- or -'4"-methylor -ethylsulfone,Z-phenylaminonaphthalene-6-sulfonic acid isopropylamide-2'-, -3 or4-sulfonic-acid amide, '2-phenylaminonaphthalene-6-sulfonic acidamide-3'-sulfonio acid methylamide, and also the-con1p0unds=of theformulae The diazo'compounds menti components in the usu naphthalenes,'5-pyrazolones j or j The new" coba soluble in'water, and are indeedmore soluble than the parent-dyestufisusedfor making them." Theyaresuit- "able for dyeing and printing ;a very wide variety of materials,but above allif or dyeing animalmaterialsfsuch as 1 silkyleather and.especially wbol," and; are; 315a suitable .for dyeing or'printingsynthetic fihers of'superpolyamides and superpolyurethanes They'are'especially suitable for dyeing'fr'orn weakly alkaline or neutral toweakly" acid, forexample, acetic acid, baths Wool 'dyeings ,so producedare distinguished by their level. character, good fastness to j 'light,and 'very good tastness' to washing, fulling, carboniz- W ng and'de'catizing. i

parts andpercentage's; being by weightfunless and These secondarynaphthylamines used as coupling components are in part known '01- can bemade by methods in themselves known. The Z-naphthylamines in question 7can be made, for example, by the method of Bucherer from the appropriate2-hydroxynaphthalenes by reaction with alkylaminesor arylaminesin-the-presence of an al-- kali bisulfite under pressure. i r

oned above, and obtainable in the. usual manner, may be coupled with thecoupling a1 manner, for example, in aneutral to acidmedium. h After thecouplingreaction the dyestufis can easily .be isolated from-the couplingmixture by filtration, since'they are generally'sparingly soluble inwater. r

. a As agents yielding cobalt for use in the processof the.

invention there come into consideration complex cobalt compounds ofaliphatic hydroxy-carboxylic acids or :dicarboxylic acids, and alsosimple cobalt salts such as'cobalt V acetate and cobalt sultate,or ifdesired CObhltihYdl'OXidBp a The treatment of the monoazo-dyestuifsobtained as described abovewith an agent; yielding cobalt 'is advan:tageously carried out in a weakly acid, neutralor espe-' cially analkaline medium. It is generally recommended to use less than one but atleast half an atomic proportion of cobalt for each molecular proportionof a mo'noazo- VThe metallization of the dyestufi is advantageouslycarried out at a' raised temperature'under atmospheric orsuperatmospheric' pressure, if desired in the presence of asuitable'addition, for example, in the presence of a salt a of anorganic acid, a base, an organic solvent-or another.

agent capable 'of assisting the formation of the complex. 7

In, one form of the process there is used as starting. material amixture ,of two different metalli'zable mono azodyestufis' of which onecorrespondslto the general Formula l above, and. the other: alsocorresponds, to the said 7 formula or is an ortho:ortho'-dihydroxymonoazo-dyestufi free from sulfonic acid and carboxylic acid groups. As

, .ortho:,ortho'-dihydroxy-rnonoazi-dyestuffs there come intoconsideration more especially those of'the benzene-a- 'acylacetic' acidamide series, and above all those which a contain an aromatically boundsulfuric acid amide group or sulfone group. Theseortho:orthd-dihydroxy-mono 13.20. dyestuffs can be made *by methods inthemselves knowntrom the diazo-components mentioned above and couplingcomponents capable of coupling in apositi'on' vicinal to anaromatically.boundhydroxyl group or an enolizable or enolized keto'g'ro'up, such ashydroxy acetic'acidarylides. I V ltiferous dyestufis of thisinventionar'e fThe following examples illustrate the invention, the."otherwise I '30 3 .25 percent;

I advantageously a'ceto -Q a stated and the relationship of parts byweight to parts by volume being the same as that of the kilogram to theliter:

Example 1 parts of sodium hydroxide, ,After the additionof parts by,vo10 solution is i of hydrochloric acid of percent'strength and 100 parts.

of ice. Into the, diamcompound sofobtained isrrun a hot solution of 30.0parts of 2-phen'ylaminonaphthalene' 13f.-sulfonie acid amide (obtained,for example, byithe and 100 parts of' dimethyl formamide, andthe wholeis 20 'stirred at 30-40 C.juntil the coupling'is complete Theprecipitated dyestutf is filtered ofi, and washedwith water and dried.It is a red powder, which dissolves, in dilute sodium hydroxide solutionwith a red coloration and in concentrated sulfuric acid with a violetcoloration j 25 4.63 parts of the dyestutf so obtai 200 parts 0 'of a 2N-solution of sodiumlhydroxide the mixture is,

j heated ,to 80 C; and mixed with '10 parts-by volume a of a cobalt,sulfate solution having a cobalt content 'ofr i A fter stirring thewhole for, fto. the metallization is'finished. The cobalt pitated bytheadditioniofsodium chloride;

It is a black powder which I bluefgreen coloration and in v lfuric.acid' with a violet colorationtand complex is ,pre'ci and filtered offand dried; dissolves in; water with a concentrated su V dyes wool from[a weakly alkalineor neutral toweakly .aceticacid bath'olivetintsjhaying' good "properties 0t fastness, a

" Example 2.

parts of sodium hydroxide, and the solution is mixed with 25 parts byvolume of a 4 N-solution of sodiuminitrite and slowly poured into 200parts of a solutionjof naph parts of hydrochloric acid of 30 percentstrength and, 1 00 temperatur coupling is 7 powder which dissolves in.dilute sodium, hydroxide 'soluationa J 4.63 part green' tintshaving'good properties oflfastr ess'g ame: folio 7 ing' tab lob 1e aregiven dditio V 15.4 parts of 4-nitro-21amino-l-hydroxybenzene aredissolved in 100 parts of waterwith the addition'of 4 lume of a4lSl-solution of sodium nitrite the ntroduced dropwise into a mixture.ch24 parts ned are dissolved in a 5 f water with the addition of l0parts by volume r l5.4 parts of. S-nitrQ-Z-ainino-l-hydroxybenzerieare'. :T dissolved in 6 0 parts of water with the addition of '4lution'of 30 partsiof .2i-I Y phenylaminonaphthalene-3'-sulfonic acid,amide in 10' 'parts of dimethylformamide isfrun' into thediafzo-suspenI 1 sion, and the whole isstirred for a tew'hou'rsl atroom, 5'

e,'and at 50,":C. in'the later 'stageguntil 'iinished; The precipitateddyestufiis filteredi oti while-hot and. washed." When dry it isablack-brown 607 V s of v the dyestufifso obtainedare suspended,

in parts ofywater and heated to SOf -C." After the addition of asolution or 0.155 .partofcobalt sulfate,: 0.fl 5 7 part of tartaric acidand 5pa'rts oticaustic, soda: solution i of TT 0 percent? strength in]50' parts .Of Water; th v whole f f 1 y The cobalti complexi is completely precipfi I 1 'tated'by the addition of sodium chlorideandiiartialneu s s ablss sr srw h'1 l 5iuii a 7 0 with; a blue;coloration ,and in 'conoentrated sulfufic acid fwith a violetcoloratiomfajhd dyesiwqolfroni weakly l falkaline; neutral or weaklyaceticgacidbatlzi'strongbluish,

lfrom'the components given in columns I ancLH, and which dye wool thetintsgiven'in colum'nIII:

3' sul fonic 'a'idtaniid'e and 4ft S parts of it hetlyestu fi fromdiazotized' 2-'amino-"1-hydroxybenzene 4 sulfonic acid iso- -I l n m 1NH:' "NH uma;

; J green.

NO OaNHCHs OH 1 5 2 NHa NH SOICHI green 2 grey.

NOr-

OH I -3 NH: NH-Q greenish blue.

N0 so NH 011 OzNUNH: NHCH: grayish green.

ozc s on a 0;NO-NH: Nnomomon Do.

SOzOHs 6 OzN NH: NH greenish olive.

rSOzNHCH:

SOzCHz The dyestufi N0. 1 of .this tableis'the' complexcobalt compoundcontaining one atom of cobalt in'complex union with 1W0 molecules of themonoazozdyestuffofthe formula SOs-NH-CH;

on NH I OzN while the dyestufl No. 6 is the complex cobalt compoundcontaining one atom of cobalt in complex union with two molecules of themonoazo dyestufi of the. formula 0H NH OzN- N=N v SOs-CH:

Example 3 4.63 parts of the dyestu'ffirom diazotized 5-nitro-2-amino-l-hydroxybenzene and Z-phenylaminonaphthalene- 75 S O rN Hg andSOrrNH-Lf-H-CH;

essence is precipitated by the addition of sodium, chloride and tion andin concentrated sulfuric acid with a brownviolet coloration, and dyeswool from a weakly alkaline 5 neutral 'or weakly acid bathgreen tints;

Similar cobalt mixed complexes are obtained by the method describedabove from the monoazo-dyestufis given in columns I andllof thefollowing table, the tints'Of 1 of an orthozorthd-dihydroxy monoazodyestufi containing a hydroxybenzene radical bound to thetazo; ,group inortho position relatively tothe'hydroxybgrou'p and a d'yest'uficf saidFormula 1. V V

2.- Axgm lgxrppbelt '9fiPQP .-9 t inie 9F? #99; of cobalt bound incomplex union witln two monoazo' dyestufis free from sulfonic andcarboxylic acid groupsand corresponding-to-theformulasg V 0.5 part :ofcobaltif erous dyestuti obtainable as described in Example 1 isdissolved in 4000 parts of water, and 100 parts rof well wettedwool areentered into the resulting dyebath at.40-50 'C. -2 parts of acetic acidof 40Ipercent strength are then added,'thebath isjraised to'th e boilin' the course of' /z houriand dying is cari- V :ried on for hour at'the boiL- Finally the wool 'is rinsed with cold water aind dried. Thereis obtained a level olive dyeing of good' fastness to'washing and'full-Practically' thevsame dyeing reproduced when'no acetic acid is adde 'dtot the dyebath. i a i 'What is claimedis: V V r f' 1; A complexcobaltrcompound containing one atom of cobaltbound in complex unionwith'twomonoazo dyestuflsfree from sulfonic'jand; carboxylic acidgroups, of

r: whichjfone contains arnenibefselected from the group consisti'ngof asulfone and a sulfonamide group bound to an aromatic nucleusofthedyestutf molecule which] corresponds to ithe formula V wherein Rrepresents a hydroxybenzene radical boundfto i" the azo linkage in orthoposition relatively' to' the hydroxyl group, Y represents amember'of thegroupconsisting of a lower 'alkyl, a lower hydroxyalkyl and a benzeneradical, and A representsa naphthalene radical bound to the azo linkage.in 1'-position and bearing the NH-Y 7 I group in 2-position, the seconddyestufi bound to the co halt atom being a memberselected'from the groupcon- 65 group andarsulfonic acid a'mide group. a 4. A complex cobaltcompound containuig one atom of cobalt boundin complexjunion two monoazodyestufis free from sulfonic and 'carboxylic acid groups,

the dyeings on wool being given in columnIII: 1O l V v R- -N=N5A- NHY 1n 7 i V V m.

V comm e 3 V 1 r V 7.; I Q V i, i r V on on or, 1 N==N V m-n-cm-oo-nnc ren} 1 V No .r co; r r V t V 7 an. i V 7 j a omacm r 7 V V NH no. 7 I OH7 0H 7 I I V V V mNHcm '2 .01 f a N=N-'c khaki.

C=N T 7 NO 7 e V r V V V b r cm i 7 r v V '7 77 a 7 ONE.

' omnom r r a 3. N=N N= s blue;

N0, N0 r m 7 V 7 7 q Example 4 wherein R represents ahydroxybenzeneradical bound to 45 a the azo linkage in ortho positionrelatively to the hydroxy group, Y 'represents a benzene radical and A anaphthalene'radical'bound to the'azo linkagein l-positionp-and bearingthe NH-Y' group 'in '2-position; at least oneof fonic acid amidegroup.;f

- 3. A complex cobalt compound co ntaining one atomf T of cobalt boundin-coniplex union withfitwo monoazo dyestufis free from, sulfonic andcarboxylic vacid groups 0 andfcorresponding to the tromula e naphthaleneradical boundtothe azo linkage in? 1 etioniand bearinglheQNH-e-Y gl'ioupin -2-pos ition, at V least one oftheradicalsik, 'A and Y containingasubsutuent'selecte'd' from the groups consistingt of a sulfone of whichonewcorresponds tothe formula 1 1 4 r coon.

' a oo-Nn-x 7' and the other to the formula 7 7 in which formulate R andR represent hydroxybenzene radicals bound to the azo linkage in orthoposition to the hydroxyl group, X and Y represent benzene radicals and Arepresents a naphthalene radical bound to the azo linkage in l-positionand bearing the NHY group in 2-position, at least one of the radicals R,A and Y containing a substituent selected from the group consisting of asulfone group and a sulfonic acid amide group.

5. A complex cobalt compound containing one atom of cobalt bound incomplex union with two monoazo dyestuifs free from sulfonic andcarboxylic acid groups and corresponding to the formula OH NH 2 whereinone Z represents a sulfonic acid amide group and the other Z a hydrogenatom.

6. A complex cobalt compound containing one atom of cobalt bound incomplex union with two monoazo dyestuffs free from sulfonic andcarboxylic acid groups, of which one corresponds to the formula COCH:

N=N-CH CO-NH-R X and the other to the formula on NHQ Ora z 2N wherein Xrepresents a sulfonic acid amide group, R represents a benzene radical,one Z represents a sulfonic acid amide group and the other Z a hydrogenatom.

7. The complex cobalt compound containing one atom of cobalt in complexunion with two molecules of the monoazo dyestufi of the formula OH NH02N SOr-NH-CE 10 8. The complex cobalt compound containing one atom ofcobalt in complex union with two molecules of the monoazo dyestutl? ofthe formula 5 OH NH ON: ON

SO2NH:

9. The complex cobalt compound containing one atom of cobalt in complexunion with two molecules of the monoazo dyestufi of the formula OH NHONON: H- H I O2-N C s Son-CH:

10. The complex cobalt compound containing one atom of cobalt in complexunion with one molecule of each of the two monoazo dyestufiscorresponding to the formulae OH NH o OzN SOs-NH-CH:

and

CO-OH: N=N-CE SOz-NH-(ilH-CH:

References Cited in the file of this patent UNITED STATES PATENTS1,823,939 Hentrich et a1 Sept. 22, 1931 2,565,898 Widmer et a1. Aug. 28,1951 2,674,515 Widmer et a1 Apr. 6, 1954 U S DEPARTMENT OF COMMERCEPATENT OFFICE CERTIFICATE OF CORRECTION Patent Non 2,824,864 4 ArthurBuehler February 25, 1958 It is hereby certified that error appears I inthe printed specification of the above numbered patent requiringcorrection and that the said Let ters Patent should read as correctedbelow;

Column 1, line 59, for sulfone acid amide" read sulfonic acid amidecolumn 2,, line 19, for "hydroxylalkyl" read vhydroxyalkyl 5 column 3,l1ne 49, for -raonoazfw" read -monoazocolumn 9, line 1;,

for "foImIl'ate" read formulae Signed and sealed this 24th day of June1958,

Attest:

KARL Ha AXLINE ROBERT C. WATSON Attesting Officer Commissioner ofPatents

1. A COMPLEX COBALT COMPOUND CONTAINING ONE ATOM OF COBALT BOUND INCOMPLEX UNION WITH TWO MONOAZO DYESTUFFS FREE FROM SULFONIC ANDCARBOXYLIC ACID GROUPS, OF WHICH ONE CONTAINS A MEMBER SELECTED FROM THEGROUP CONSISTING OF A SULFONE AND A SULFONAMIDE GROUP BOUND TO ANAROMATIC NUCLEOUS OF THE DYESTUFF MOLECULE WHICH CORRESPONDS TO THEFORMULA